Light emitting device

ABSTRACT

A light emitting device is disclosed. The light emitting device may include a light emitting diode (LED) for emitting light and phosphor adjacent to the LED. The phosphor may be excitable by light emitted by the LED and may include a first compound having a host lattice comprising first ions and oxygen. In one embodiment, the host lattice may include silicon, the copper ions may be divalent copper ions and first compound may have an Olivin crystal structure, a β-K2SO4 crystal structure, a trigonal Glaserite (K 3 Na(SO 4 ) 2 ) or monoclinic Merwinite crystal structure, a tetragonal Ackermanite crystal structure, a tetragonal crystal structure or an orthorhombic crystal structure. In another embodiment, the copper ions do not act as luminescent ions upon excitation with the light emitted by the LED.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 11/948,845, filed on Nov. 30, 2007, now U.S. Pat. No.8,066,909, which is a continuation-in-part of U.S. patent applicationSer. No. 11/024,702, filed on Dec. 30, 2004, now U.S. Pat. No.7,554,129, the disclosures of which are incorporated by reference hereinin their entirety, which claim priority of Korean Patent Application No.2004-042396, filed Jun. 10, 2004, the disclosure of which isincorporated by reference herein in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the present invention relate generally to light emittingdevices and, more particularly, to light emitting devices including atleast one light-emitting diode and phosphor including lead- and/orcopper-containing chemical compounds and converting the wavelength oflight.

2. Description of the Related Art

Light emitting devices (LEDs), which used to be used for electronicdevices, are now used for automobiles and illumination products. Sincelight emitting devices have superior electrical and mechanicalcharacteristics, demands for light emitting devices have been increased.In connection to this, interests in white LEDs are increasing as analternative to fluorescent lamps and incandescent lamps.

In LED technology, solution for realization of white light is proposedvariously. Normally, realization of white LED technology is to put thephosphor on the light-emitting diode, and mix the primary emission fromthe light emitting diode and the secondary emission from the phosphor,which converts the wavelength. For example, as shown in WO 98/05078 andWO 98/12757, use a blue light emitting diode, which is capable ofemitting a peak wavelength at 450-490 nm, and YAG group material, whichabsorbs light from the blue light emitting diode and emits yellowishlight (mostly), which may have different wavelength from that of theabsorbed light. However, phosphors which are used for white LEDs areusually unstable in the water, vapor or polar solvent, and thisunstableness may cause changes in the emitting characteristics of whiteLED.

SUMMARY OF THE INVENTION

One embodiment exemplarily described herein can be generallycharacterized as a light emitting device that includes a light emittingdiode (LED) for emitting light and a phosphor adjacent to the LED. Thephosphor is excitable by light emitted by the LED and may include afirst compound having a host lattice comprising first ions, silicon andoxygen. A first portion of the first ions may be substituted by divalentcopper ions and the first compound may have one of an Olivin crystalstructure, a β-K₂SO₄ crystal structure, a trigonal Glaserite(K₃Na(SO₄)₂) or monoclinic Merwinite crystal structure, a tetragonalAckermanite crystal structure, a tetragonal crystal structure and anorthorhombic crystal structure.

Another embodiment exemplarily described herein can be generallycharacterized as a light emitting device that includes a light emittingdiode (LED) for emitting light and a phosphor adjacent to the LED. Thephosphor is excitable by light emitted by the LED and may include afirst compound having a host lattice comprising first ions and oxygen. Afirst portion of the first ions may be substituted by copper ions andthe copper ions do not act as luminescent ions upon excitation with thelight emitted by the LED.

BRIEF DESCRIPTION OF THE DRAWINGS

Further embodiments of the invention may be apparent upon considerationof the following detailed description, taken in conjunction with theaccompanying drawings, in which like reference characters refer to likeparts throughout, and in which:

FIG. 1 shows a side cross-sectional view of an illustrative embodimentof a portion of a chip-type package light emitting device;

FIG. 2 shows a side cross-sectional view of an illustrative embodimentof a portion of a top-type package light emitting device;

FIG. 3 shows a side cross-sectional view of an illustrative embodimentof a portion of a lamp-type package light emitting device;

FIG. 4 shows a side cross-sectional view of an illustrative embodimentof a portion of a light emitting device for high power;

FIG. 5 shows a side cross-sectional view of another illustrativeembodiment of a portion of a light emitting device for high power;

FIG. 6 shows emitting spectrum of a light emitting device withluminescent material; and

FIG. 7 shows emitting spectrum of the light emitting device withluminescent material according to another embodiment.

DETAILED DESCRIPTION

Refer to the attached drawing, the wavelength conversion light emittingdevice is going to be explained in detail, and the light emitting deviceand the phosphor are separately explained for easiness of explanation asbelow.

(Light Emitting Device)

FIG. 1 shows a side cross-sectional view of an illustrative embodimentof a portion of a chip-type package light emitting device. The chip-typepackage light emitting device may comprise at least one light emittingdiode and a phosphorescent substance. Electrodes 5 may be formed on bothsides of substrate 1. Light emitting diode 6 emitting light may bemounted on one of the electrodes 5. Light emitting diode 6 may bemounted on electrode 5 through electrically conductive paste 9. Anelectrode of light emitting diode 6 may be connected to electrodepattern 5 via an electrically conductive wire 2.

Light emitting diodes may emit light with a wide range of wavelengths,for example, from ultraviolet light to visible light. In one embodiment,a UV light emitting diode and/or blue light emitting diode may be use.

Phosphor, i.e., a phosphorescent substance, 3 may be placed on the topand side faces of the light emitting diode 6. In some embodiments, thephosphor may include lead- and/or copper containing chemical compounds.In some embodiments, the chemical compounds may comprise aluminates,silicates, antimonates, germanates, germanate-silicates, phosphates, orthe like, or a combination thereof. Phosphor 3 converts the wavelengthof the light from the light emitting diode 6 to another wavelength orother wavelengths. In one embodiment, the light is in a visible lightrange after the conversion. Phosphor 3 may be applied to light emittingdiode 6 after mixing phosphor 3 with a hardening resin. The hardeningresin including phosphor 3 may also be applied to the bottom of lightemitting diode 6 after mixing phosphor 3 with electrically conductivepaste 9.

The light emitting diode 6 mounted on substrate 1 may be sealed with oneor more sealing materials 10. Phosphor 3 may be placed on the top andside faces of light emitting diode 6. The sealing material 10 may coverthe light emitting diode 6 and the phosphor 3. Phosphor 3 can also bedistributed in the hardened sealing material during the production. Sucha manufacturing method is described in U.S. Pat. No. 6,482,664, which ishereby incorporated by reference in its entirety.

Phosphor 3 may comprise one or more lead- and/or copper containingchemical compounds. Phosphor 3 may include one or more single chemicalcompounds. Each single compound may have an emission peak of, forexample, from about 440 nm to about 500 nm, from about 500 nm to about590 nm, or from about 580 nm to 700 nm. Phosphor 3 may include one ormore single phosphors, which may have an emission peak as exemplifiedabove.

In regard to light emitting device 40, light emitting diode 6 may emitprimary light when light emitting diode 6 receives power from a powersupply. The primary light then may stimulate phosphor(s) 3, andphosphor(s) 3 may convert the primary light to a light with longerwavelength(s) (a secondary light). The primary light from the lightemitting diode 6 and the secondary light from the phosphors 3 arediffused and mixed together so that a predetermined color of light invisible spectrum may be emitted from light emitting diode 6. In oneembodiment, more than one light emitting diodes that have differentemission peaks can be mounted together. In some embodiments, a mixtureratio of different phosphors can be adjusted to achieve a desired colorof light, color temperature, and CRI.

As described above, if the light emitting diode 6 and the compound(s)included in phosphor 3 are properly controlled then the desired colortemperature or specific color coordination can be provided, especially,wide range of color temperature, for example, from about 2,000K to about8,000K or about 10,000K and/or color rendering index of greater thanabout 60. In some embodiments, the compound(s) included in the phosphor3 can be controlled to have a color rendering index between about 50 andabout 90. In some embodiments, the compound(s) included in the phosphor3 can be controlled to have a color rendering index greater than about90. In some embodiments, the compound(s) included in the phosphor 3 canbe controlled to have a color rendering index between about 90 and about95. Therefore, the light emitting devices exemplarily described hereinmay be used for electronic devices such as home appliances, stereos,telecommunication devices, and for interior/exterior custom displays.The light emitting devices exemplarily described herein may also be usedfor automobiles and illumination products because they provide similarcolor temperatures and CRI to those of the visible light.

FIG. 2 shows a side cross-sectional view of an illustrative embodimentof a portion of a top-type package light emitting device. A top-typepackage light emitting device may have a similar structure as that ofthe chip type package light emitting device 40 of FIG. 1. The top-typepackage device may have reflector 31 which may reflect the light fromthe light emitting diode 6 to the desire direction.

In top-type package light emitting device 50, more than one lightemitting diodes can be mounted. Each of such light emitting diodes mayhave a different peak wavelength from that of others. Phosphor 3 maycomprise a plurality of single compounds with different emission peaks.The proportion of each of such plurality of compounds may be regulated.Such a phosphor may be applied to the light emitting diode and/oruniformly distributed in the hardening material of the reflector 31. Asexplained more fully below, the phosphor may include lead- and/or coppercontaining aluminate type compounds, lead- and/or copper containingsilicates, lead- and/or copper containing antimonates, lead- and/orcopper containing germanates, lead- and/or copper containinggermanate-silicates, lead and/or copper containing phosphates, or anycombination thereof.

In one embodiment, the light emitting device of the FIG. 1 or FIG. 2 caninclude a metal substrate, which may have good heat conductivity. Such alight emitting device may easily dissipate the heat from the lightemitting diode. Therefore, light emitting devices for high power may bemanufactured. If a heat sink is provided beneath the metal substrate,the heat from the light emitting diode may be dissipated moreeffectively.

FIG. 3 shows a side cross-sectional view of an illustrative embodimentof a portion of a lamp-type package light emitting device. Lamp typelight emitting device 60 may have a pair of leads 51, 52, and a diodeholder 53 may be formed at the end of one lead. Diode holder 53 may havea shape of cup, and one or more light emitting diodes 6 may provided inthe diode holder 53. When a number of light emitting diodes are providedin the diode holder 53, each of them may have a different peakwavelength from that of others. An electrode of light emitting diode 6may be connected to lead 52 by, for example, electrically conductivewire 2.

Regular volume of phosphor 3, which may be mixed in the epoxy resin, maybe provided in diode holder 53. As explained more fully below, phosphor3 may include lead- and/or copper containing components.

Moreover, the diode holder may include the light emitting diode 6 andthe phosphor 3 may be sealed with hardening material such as epoxy resinor silicon resin.

In one embodiment, the lamp type package light emitting device may havemore than one pair of electrode pair leads. In another embodiment, alight emitting device may comprise a plurality of electrodes arranged ona substrate, an electrically conductive device connecting a lightemitting diode with one of the plurality of electrodes, the lightemitting diode being arranged on another of the plurality of electrodes.In another embodiment of, a light emitting device may comprise aplurality of leads, a diode holder arranged at the end of one of theplurality of leads, and an electrically conductive device connected to alight emitting diode with another of the plurality of leads. The lightemitting diode may be arranged in the diode holder and comprise aplurality of electrodes.

FIG. 4 shows a side cross-sectional view of an illustrative embodimentof a portion of a light emitting device for high power. Heat sink 71 maybe provided inside of housing 73 of the light emitting device for highpower 70, and it may be partially exposed to outside. A pair of leadframes 74 may protrude from housing 73.

One or more light emitting diodes may be mounted directly on one leadframe 74, and an electrode of the light emitting diode 6 and anotherlead frame 74 may be connected via electrically conductive wire. Inanother embodiment, one or more light emitting diodes may be mounteddirectly on the heat sink 71, as opposed to directly on the lead frame74, via thermally conductive adhesive. Electrically conductive pate 9may be provided between light emitting diode 6 and lead frame 74. Thephosphor 3 may be placed on top and side faces of light emitting diode6.

FIG. 5 shows a side cross-sectional view of another illustrativeembodiment of a portion of a light emitting device for high power.

Light emitting device for high power 80 may have housing 63, which maycontain light emitting diodes 6, 7, phosphor 3 arranged on the top andside faces of light emitting diodes 6, 7, one or more heat sinks 61, 62,and one or more lead frames 64. In one embodiment, one or more lightemitting diodes 6, 7 may be mounted directly on one or more of the heatsinks 61, 62 via thermally conductive adhesive. In one or more of thelead frames 64. The lead frames 64 may receive power from a powersupplier and may protrude from housing 63. In another embodiment, alight emitting device comprises a housing, a heat sink at leastpartially arranged in the housing, a plurality of lead frames arrangedon or around the heat sink, and an electrically conductive deviceconnecting the light emitting diode with one of the plurality of leadframes. The light emitting diode may be arranged on the heat sink.

In the light emitting devices for high power 70, 80 in the FIGS. 4 and5, the phosphor 3 can be added to the paste, which may be providedbetween heat sink and light emitting devices. A lens may be combinedwith housing 63, 73.

In a light emitting device for high power, one or more light emittingdiodes can be used selectively and the phosphor can be regulateddepending on the light emitting diode. As explained more fully below,the phosphor may include lead and/or copper containing components.

A light emitting device for high power may have a radiator (not shown)and/or heat sink(s). Air or a fan may be used to cool the radiator.

The light emitting devices exemplarily described herein are not limitedto the structures described above, and the structures can be modifieddepending on the characteristics of light emitting diodes, phosphor,wavelength of light, and also applications. Moreover, new part can beadded to the structures.

Exemplary embodiments of the phosphor 3 are described as follows.

(Phosphor)

According to some embodiments, the phosphor 3 may include one or morelead- and/or copper containing chemical compounds. The phosphor 3 may beexcited by UV and/or visible (e.g., blue) light, and emit light due totransitions of the direct type, f-d transitions, or charge transfertransitions. In some embodiments, the lead- and/or copper-containingchemical compounds may be generally characterized as including a hostlattice having anions and cations. In some embodiments, at least aportion of the cations are divalent cations. In some embodiments, thedivalent cations include alkaline earth ions. In some embodiments, atleast a portion of the divalent cations of the host lattice aresubstituted by divalent lead and/or divalent copper ions. Thus, a firstportion of first ions within the host lattice may be substituted bydivalent copper ions.

As mentioned above, conventional luminescent materials and phosphors aregenerally unstable in water, air humidity, water steam and polarsolvents. However, due to a higher covalency and a lower basicity, thesubstitutionally-incorporated divalent lead and/or divalent copper ionsin the host lattice of the chemical compound yields luminescentmaterials have improved resistance against water, air humidity and polarsolvents. Moreover, it will be appreciated that the divalent lead and/ordivalent copper ions within the host lattice do not act as activators(also referred to herein as “luminescent center ions”) and, therefore donot luminesce.

As described above, the phosphor 3 may include one or more chemicalcompounds such as, for example, aluminates, silicates, antimonates,germanates, germanate-silicates, and/or phosphates. Exemplaryembodiments of these chemical compounds are described in greater detailbelow.

In some embodiments, the lead- and/or copper-containing aluminates maybe generally characterized according to formulas (1), (2), and (5)a(M′O).b(M″₂O).c(M″X).d(Al₂O₃).e(M′″O).f(M″″₂O₃).g(M′″″_(o)O_(p)).h(M″″″_(x)O_(y))  (1)

wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be oneor more monovalent elements, for example, Li, Na, K, Rb, Cs, Au, Ag,and/or any combination thereof; M′″ may be one or more divalentelements, for example, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or anycombination thereof; M″″ may be one or more trivalent elements, forexample, Sc, B, Ga, In, and/or any combination thereof; M′″″ may be Si,Ge, Ti, Zr, Mn, V, Nb, Ta, W, Mo, and/or any combination thereof; M″″″may be Bi, Sn, Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho,Er, Tm, Yb, Lu, and/or any combination thereof, X may be F, Cl, Br, I,and/or any combination thereof; 0≦a≦2; 0≦b≦2; 0≦c≦2; 0<d≦8; 0<e≦4;0≦f≦3; 0≦g≦8; 0≦h≦2; 1≦o≦2; 1≦p≦5; 1≦x≦2; and 1≦y≦5.a(M′O).b(M″₂O)c(M″X)4-a-b-c(M′″O)7(Al₂O₃)d(B₂O₃)e(Ga₂O₃)f(SiO₂)g(GeO₂)h(M″″_(x)O_(y))  (2)

wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be oneor more monovalent elements, for example, Li, Na, K, Rb, Cs, Au, Ag,and/or any combination thereof; M′″ may be one or more divalentelements, for example, Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or anycombination thereof; M″″ may be Bi, Sn, Sb, Sc, Y, La, In, Ce, Pr, Nd,Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and any combination thereof,X may be F, Cl, Br, I, and any combination thereof; 0<a≦4; 0≦b≦2; 0≦c≦2;0≦d≦1; 0≦e≦1; 0≦f≦1; 0≦g≦1; 0<h≦2; 1≦x≦2; and 1≦y≦5.

The preparation of copper—as well as lead containing luminescentmaterials may be a basic solid state reaction. Pure starting materialswithout any impurities, e.g. iron, may be used.

Any starting material which may transfer into oxides via a heatingprocess may be used to form oxygen dominated phosphors.

Examples of Preparation

Preparation of the luminescent material having formula (3)Cu_(0.02)Sr_(3.98)Al₁₄O₂₅:Eu  (3)

Starting materials: CuO, SrCO₃, Al(OH)₃, Eu₂O₃, and/or any combinationthereof.

The starting materials in the form of oxides, hydroxides, and/orcarbonates may be mixed in stoichiometric proportions together withsmall amounts of flux, e.g., H₃BO₃. The mixture may be fired in analumina crucible in a first step at about 1,200° C. for about one hour.After milling the pre-fired materials a second firing step at about1,450° C. in a reduced atmosphere for about 4 hours may be followed.After that the material may be milled, washed, dried and sieved. Theresulting luminescent material may have an emission maximum of about 494nm.

TABLE 1 copper-containing Eu²⁺-activated aluminate compared withEu²⁺-activated aluminate without copper at about 400 nm excitationwavelength Copper doped compound Compound without copperCu_(0.02)Sr_(3.98)Al₁₄O₂₅:Eu Sr₄Al₁₄O₂₅:Eu Luminous density 103.1 100(%) Wavelength (nm) 494 493

Preparation of the luminescent material having formula (4)Pb_(0.05)Sr_(3.95)Al₁₄O₂₅:Eu  (4)

Starting materials: PbO, SrCO₃, Al₂O₃, Eu₂O₃, and/or any combinationthereof.

The starting materials in form of very pure oxides, carbonates, or othercomponents which may decompose thermally into oxides, may be mixed instoichiometric proportion together with small amounts of flux, forexample, H₃BO₃. The mixture may be fired in an alumina crucible at about1,200° C. for about one hour in the air. After milling the pre-firedmaterials a second firing step at about 1,450° C. in air for about 2hours and in a reduced atmosphere for about 2 hours may be followed.Then the material may be milled, washed, dried, and sieved. Theresulting luminescent material may have an emission maximum of fromabout 494.5 nm.

TABLE 2 lead-containing Eu²⁺-activated aluminate compared withEu²⁺-activated aluminate without lead at about 400 nm excitationwavelength Lead-containing compound Compound without leadPb_(0.05)Sr_(3.95)Al₁₄O₂₅:Eu Sr₄Al₁₄O₂₅:Eu Luminous density (%) 101.4100 Wavelength (nm) 494.5 493

TABLE 3 optical properties of some copper- and/or lead doped aluminatesexcitable by long wave ultraviolet and/or by visible light and theirluminous density in % at 400 nm excitation wavelength Luminous densityat 400 nm Peak wave Peak wave excitation length of length of comparedwith lead-/copper- materials Possible compounds not containing withoutexcitation containing materials lead/copper Composition range(nm)copper/lead (%) (nm) (nm) Cu_(0.5)Sr_(3.5)Al₁₄O₂₅:Eu 360-430 101.2 495493 Cu_(0.02)Sr_(3.98)Al₁₄O₂₅:Eu 360-430 103.1 494 493Pb_(0.05)Sr_(3.95)Al₁₄O₂₅:Eu 360-430 101.4 494.5 493Cu_(0.01)Sr_(3.99)Al_(13.995)Si_(0.005)O₂₅:Eu 360-430 103 494 492Cu_(0.01)Sr_(3.395)Ba_(0.595)Al₁₄O₂₅:Eu, 360-430 100.8 494 493 DyPb_(0.05)Sr_(3.95)Al_(13.95)Ga_(0.05)O₂₅:Eu 360-430 101.5 494 494a(M′O).b(M″O).c(Al₂O₃).d(M′″₂O₃).e(M″″O₂).f(M″″_(x)O_(y))  (5)

wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be Be,Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M′″ may beB, Ga, In, and/or any combination thereof; M″″ may be Si, Ge, Ti, Zr,Hf, and/or any combination thereof; M′″″ may be Bi, Sn, Sb, Sc, Y, La,Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and/or anycombination thereof; 0<a≦1; 0≦b≦2; 0≦c≦8; 0≦d≦1; 0≦e≦1; 0<f≦2; 1≦x≦2;and 1≦y≦5.

Example of Preparation

Preparation of the luminescent material having formula (6)Cu_(0.05)Sr_(0.95)Al_(1.9997)Si_(0.0003)O₄:Eu  (6)

Starting materials: CuO, SrCO₃, Al₂O₃, SiO₂, Eu₂O₃, and/or anycombination thereof.

The starting materials in the form of, for example, pure oxides and/oras carbonates may be mixed in stoichiometric proportions together withsmall amounts of flux, for example, AlF₃. The mixture may be fired in analumina crucible at about 1,250° C. in a reduced atmosphere for about 3hours. After that the material may be milled, washed, dried and sieved.The resulting luminescent material may have an emission maximum of about521.5 nm.

TABLE 4 copper-containing Eu²⁺-activated aluminate compared withEu²⁺-activated aluminate without copper at about 400 nm excitationwavelength Compound Copper-containing compound without copperCu_(0.05)Sr_(0.95)Al_(1.9997)Si_(0.0003)O₄:Eu SrAl₂O₄:Eu Luminousdensity (%) 106 100 Wavelength (nm) 521.5 519

Preparation of the luminescent material having formula (7)Cu_(0.12)BaMg_(1.88)Al₁₆O₂₇:Eu  (7)

Starting materials: CuO, MgO, BaCO₃, Al(OH)₃, Eu₂O₃, and/or anycombination thereof.

The starting materials in the form of, for example, pure oxides,hydroxides, and/or carbonates may be mixed in stoichiometric proportionstogether with small amounts of flux, for example, AlF₃. The mixture maybe fired in an alumina crucible at about 1,420° C. in a reducedatmosphere for about 2 hours. After that the material may be milled,washed, dried, and sieved. The resulting luminescent material may havean emission maximum of about 452 nm.

TABLE 5 copper-containing Eu²⁺-activated aluminate compared with coppernot doped Eu²⁺-activated aluminate at 400 nm excitation wavelengthCopper-containing Comparison compound without copperCu_(0.12)BaMg_(1.88)Al₁₆O₂₇:Eu BaMg₂Al₁₆O₂₇:Eu Luminous density (%) 101100 Wavelength (nm) 452 450

Preparation of the luminescent material having formula (8)Pb_(0.1)Sr_(0.9)Al₂O₄:Eu  (8)

Starting materials: PbO, SrCO₃, Al(OH)₃, Eu₂O₃, and/or any combinationthereof.

The starting materials in form of, for example, pure oxides, hydroxides,and/or carbonates may be mixed in stoichiometric proportions togetherwith small amounts of flux, for example, H₃BO₃. The mixture may be firedin an alumina crucible at about 1,000° C. for about 2 hours in the air.After milling the pre-fired materials a second firing step at about1,420° C. in the air for about 1 hour and in a reduced atmosphere forabout 2 hours may be followed. After that the material may be milled,washed, dried and sieved. The resulting luminescent material may have anemission maximum of about 521 nm.

TABLE 6 lead-containing Eu²⁺-activated aluminate compared withEu²⁺-activated aluminate without lead at about 400 nm excitationwavelength Lead-containing Compound compound without leadPb_(0.1)Sr_(0.9)Al₂O₄:Eu SrAl₂O₄:Eu Luminous density (%) 102 100Wavelength(nm) 521 519

Results obtained in regard to copper- and/or lead doped aluminates areshown in table 7.

TABLE 7 optical properties of some copper- and/or lead doped aluminatesexcitable by long wave ultraviolet and/or by visible light and theirluminous density in % at 400 nm excitation wavelength Luminous densityat 400 nm excitation Peak wave Possible compared with length of lead-/excitation compounds not copper- Peak wave length of range containingcontaining materials without Composition (nm) copper/lead (%) materials(nm) lead/copper (nm) Cu_(0.05)Sr_(0.95)Al_(1.9997)Si_(0.0003)O₄:Eu360-440 106   521.5 519Cu_(0.2)Mg_(0.7995)Li_(0.0005)Al_(1.9)Ga_(0.1)O₄:Eu, 360-440 101.2 482480 Dy Pb_(0.1)Sr_(0.9)Al₂O₄:Eu 360-440 102 521 519Cu_(0.05)BaMg_(1.95)Al₁₆O₂₇:Eu, Mn 360-400 100.5 451, 515 450, 515Cu_(0.12)BaMg_(1.88)Al₁₆O₂₇:Eu 360-400 101 452 450Cu_(0.01)BaMg_(0.99)Al₁₀O₁₇:Eu 360-400 102.5 451 449Pb_(0.1)BaMg_(0.9)Al_(9.5)Ga_(0.5)O₁₇:Eu, Dy 360-400 100.8 448 450Pb_(0.08)Sr_(0.902)Al₂O₄:Eu, Dy 360-440 102.4 521 519Pb_(0.2)Sr_(0.8)Al₂O₄:Mn 360-440 100.8 658 655Cu_(0.06)Sr_(0.94)Al₂O₄:Eu 360-440 102.3 521 519Cu_(0.05)Ba_(0.94)Pb_(0.06)Mg_(0.95)Al₁₀O₁₇:Eu 360-440 100.4 451 449Pb_(0.3)Ba_(0.7)Cu_(0.1)Mg_(1.9)Al₁₆O₂₇:Eu 360-400 100.8 452 450Pb_(0.3)Ba_(0.7)Cu_(0.1)Mg_(1.9)Al₁₆O₂₇:Eu, 360-400 100.4 452, 515 450,515 Mn

In some embodiments, the lead- and/or copper-containing silicates may begenerally characterized according to formula (9)a(M′O).b(M″O).c(M′″X)).d(M′″₂O).e(M″″₂O₃).f(M′″″_(o)O_(p)).g(SiO₂).h(M″″″_(x)O_(y))  (9)

wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be Be,Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M′″ may beLi, Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M″″ may beAl, Ga, In, and/or any combination thereof; M′″″ may be Ge, V, Nb, Ta,W, Mo, Ti, Zr, Hf, and/or any combination thereof; M″″″ may be Bi, Sn,Sb, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu,and/or any combination thereof; X may be F, Cl, Br, I, and anycombination thereof; 0<a≦2; 0<b≦8; 0≦c≦4; 0≦d≦2; 0≦e≦2; 0≦f≦2; 0<g≦10;0<h≦5; 1≦o≦2; 1≦p≦5; 1≦x≦2; and 1≦y≦5.

The copper-containing silicates exemplarily described herein may, insome embodiments, contain SiO₄ and can be characterized as having anOlivin structure (orthorhombic) or β-K₂SO₄ structure (orthorhombic);contain Si₂O₈ and be characterized as having a trigonal Glaserite(K₃Na(SO₄)₂) or monoclinic Merwinite structure; contain Si₂O₇ and becharacterized as having a tetragonal Ackermanite structure; contain SiO₅and be characterized as having a tetragonal structure; and/or containSi₂O₅ and be characterized as having an orthorhombic structure.

Example of Preparation

Preparation of the luminescent material having formula (10)Cu_(0.05)Sr_(1.7)Ca_(0.25)SiO₄:Eu  (10)

Starting materials: CuO, SrCO₃, CaCO₃, SiO₂, Eu₂O₃, and/or anycombination thereof.

The starting materials in the form of pure oxides and/or carbonates maybe mixed in stoichiometric proportions together with small amounts offlux, for example NH₄Cl. The mixture may be fired in an alumina crucibleat about 1,200° C. in an inert gas atmosphere (e.g., N₂ or noble gas)for about 2 hours. Then the material may be milled. After that, thematerial may be fired in an alumina crucible at about 1,200° C. in aslightly reduced atmosphere for about 2 hours. Then, the material may bemilled, washed, dried, and sieved. The resulting luminescent materialmay have an emission maximum at about 592 nm.

TABLE 8 copper-containing Eu²⁺-activated silicate compared withEu²⁺-activated silicate without copper at about 400 nm excitationwavelength Copper-containing Compound compound without copperCu_(0.05)Sr_(1.17)Ca_(0.25)SiO₄:Eu Sr_(1.7)Ca_(0.3)SiO₄:Eu Luminousdensity (%) 104 100 Wavelength(nm) 592 588

Preparation of the Luminescent Material Having Formula (11):Cu_(0.2)Ba₂Zn_(0.2)Mg_(00.6)Si₂O₇:Eu  (11)

Starting materials: CuO, BaCO₃, ZnO, MgO, SiO₂, Eu₂O₃, and/or anycombination thereof.

The starting materials in the form of very pure oxides and carbonatesmay be mixed in stoichiometric proportions together with small amountsof flux, for example, NH₄Cl. In a first step the mixture may be fired inan alumina crucible at about 1,100° C. in a reduced atmosphere for about2 hours. Then the material may be milled. After that the material may befired in an alumina crucible at about 1,235° C. in a reduced atmospherefor about 2 hours. Then that the material may be milled, washed, driedand sieved. The resulting luminescent material may have an emissionmaximum at about 467 nm.

TABLE 9 copper-containing Eu²⁺-activated silicate compared withEu²⁺-activated silicate without copper at 400 nm excitation wavelengthCompound Copper-containing compound without copperCu_(0.2)Sr₂Zn_(0.2)Mg_(0.6)Si₂O₇:Eu Sr₂Zn₂Mg_(0.6)Si₂O₇:Eu Luminousdensity 101.5 100 (%) Wavelength (nm) 467 465

Preparation of the luminescent material having formula (12)Pb_(0.1)Ba_(0.95)Sr_(0.95)Si_(0.998)Ge_(0.002)O₄:Eu  (12)

Starting materials: PbO, SrCO₃, BaCO₃, SiO₂, GeO₂, Eu₂O₃, and/or anycombination thereof

The starting materials in the form of oxides and/or carbonates may bemixed in stoichiometric proportions together with small amounts of flux,for example, NH₄Cl. The mixture may be fired in an alumina crucible atabout 1,000° C. for about 2 hours in the air. After milling thepre-fired materials a second firing step at 1,220° C. in air for 4 hoursand in reducing atmosphere for 2 hours may be followed. After that thematerial may be milled, washed, dried and sieved. The resultingluminescent material may have an emission maximum at about 527 nm.

TABLE 10 lead-containing Eu²⁺-activated silicate compared withEu²⁺-activated silicate without lead at about 400 nm excitationwavelength Compound Lead-containing compound without leadPb_(0.1)Ba_(0.95)Sr_(0.95)Si_(0.998)Ge_(0.002)O₄:Eu BaSrSiO₄:Eu Luminous101.3 100 density (%) Wavelength (nm) 527 525

Preparation of the luminescent material having formula (13)Pb_(0.25)Sr_(3.75)Si₃O₈Cl₄:Eu  (13)

Starting materials: PbO, SrCO₃, SrCl₂ SiO₂, Eu₂O₃, and any combinationthereof.

The starting materials in the form of oxides, chlorides, and/orcarbonates may be mixed in stoichiometric proportions together withsmall amounts of flux, for example, NH₄Cl. The mixture may be fired inan alumina crucible in a first step at about 1,100° C. for about 2 hoursin the air. After milling the pre-fired materials a second firing stepat about 1,220° C. in the air for about 4 hours and in a reducedatmosphere for about 1 hour may be followed. After that the material maybe milled, washed, dried and sieved. The resulting luminescent materialmay have an emission maximum at about 492 nm.

TABLE 11 lead-containing Eu²⁺-activated chlorosilicate compared withEu²⁺- activated chlorosilicate without lead at 400 nm excitationwavelength Lead-containing compound Compound without leadPb_(0.25)Sr_(3.75)Si₃O₈Cl₄:Eu Sr₄Si₃O₈Cl₄:Eu Luminous density 100.6 100(%) Wavelength (nm) 492 490

Results obtained with respect to copper- and/or lead-containingsilicates are shown in table 12.

TABLE 12 optical properties of some copper- and/or lead-containing rareearth activated silicates excitable by long wave ultraviolet and/or byvisible light and their luminous density in % at about 400 nm excitationwavelength Luminous density at 400 nm excitation Peak wave compared withlength of Possible compounds not Peak wave materials excitationcontaining length of lead-/ without range copper/lead copper-dopedlead/copper Composition (nm) (%) materials (nm) (nm)Pb_(0.1)Ba_(0.95)S_(r0.95)Si_(0.998)Ge_(0.002)O₄:Eu 360-470 101.3 527525 Cu_(0.02)(Ba,Sr,Ca,Zn)_(1.98)SiO₄:Eu 360-500 108.2 565 560Cu_(0.05)Sr_(1.7)Ca_(0.25)SiO₄:Eu 360-470 104 592 588Cu_(0.05)Li_(0.002)Sr_(1.5)Ba_(0.448)SiO₄:Gd, 360-470 102.5 557 555 EuCu_(0.2)Sr₂Zn_(0.2)Mg_(0.6)Si₂O₇:Eu 360-450 101.5 467 465Cu_(0.02)Ba_(2.8)Sr_(0.2)Mg_(0.98)Si₂O₈:Eu, 360-420 100.8 440, 660 438,660 Mn Pb_(0.25)Sr_(3.75)Si₃O₈Cl₄:Eu 360-470 100.6 492 490Cu_(0.2)Ba_(2.2)Sr_(0.75)Pb_(0.05)Zn_(0.8)Si₂O₈:Eu 360-430 100.8 448 445Cu_(0.2)Ba₃Mg_(0.8)Si_(1.99)Ge_(0.01)O₈:Eu 360-430 101 444 440Cu_(0.5)Zn_(0.5)Ba₂Ge_(0.2)Si_(1.8)O₇:Eu 360-420 102.5 435 433Cu_(0.8)Mg_(0.2)Ba₃Si₂O₈:Eu, Mn 360-430 103 438, 670 435, 670Pb_(0.15)Ba_(1.84)Zn_(0.01)Si_(0.99)Zr_(0.01)O₄:Eu 360-500 101 512 510Cu_(0.2)Ba₅Ca_(2.8)Si₄O₁₆:Eu 360-470 101.8 495 491

In some embodiments, the lead- and/or copper-containing antimonates maybe generally characterized according to formula (14)a(M′O).b(M″₂O).c(M″X).d(Sb₂O₅).e(M′″O).f(M″″_(x)O_(y))  (14)

wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be Li,Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M′″ may be Be,Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M″″ may beBi, Sn, Sc, Y, La, Pr, Sm, Eu, Tb, Dy, Gd, and/or any combinationthereof; X may be F, Cl, Br, I, and/or any combination thereof; 0<a≦2;0≦b≦2; 0≦c≦4; 0<d≦8; 0≦e≦8; 0≦f≦2; 1≦x≦2; and 1≦y≦5.

Examples of Preparation

Preparation of the luminescent material having formula (15)Cu_(0.2)Mg_(1.7)Li_(0.2)Sb₂O₇:Mn  (15)

Starting materials: CuO, MgO, Li₂O, Sb₂O₅, MnCO₃, and/or any combinationthereof.

The starting materials in the form of oxides may be mixed instoichiometric proportion together with small amounts of flux. In afirst step the mixture may be fired in an alumina crucible at about 985°C. in the air for about 2 hours. After pre-firing the material may bemilled again. In a second step the mixture may be fired in an aluminacrucible at about 1,200° C. in an atmosphere containing oxygen for about8 hours. After that the material may be milled, washed, dried andsieved. The resulting luminescent material may have an emission maximumat about 626 nm.

TABLE 13 copper-containing antimonate compared with antimonate withoutcopper at about 400 nm excitation wavelength ComparisonCopper-containing compound without copperCu_(0.2)Mg_(1.7)Li_(0.2)Sb₂O₇:Mn Mg₂Li_(0.2)Sb₂O₇:Mn Luminous density101.8 100 (%) Wavelength (nm) 652 650

Preparation of the luminescent material having formula (16)Pb_(0.006)Ca_(0.6)Sr_(0.394)Sb₂O₆  (16)

Starting materials: PbO, CaCO₃, SrCO₃, Sb₂O₅, and/or any combinationthereof.

The starting materials in the form of oxides and/or carbonates may bemixed in stoichiometric proportions together with small amounts of flux.In a first step the mixture may be fired in an alumina crucible at about975° C. in the air for about 2 hours. After pre-firing the material maybe milled again. In a second step the mixture may be fired in an aluminacrucible at about 1,175° C. in the air for about 4 hours and then in anoxygen-containing atmosphere for about 4 hours. After that the materialmay be milled, washed, dried and sieved. The resulting luminescentmaterial may have an emission maximum at about 637 nm.

TABLE 14 lead-containing antimonate compared with antimonate withoutlead at 400 nm excitation wavelength Lead-containing compound Compoundwithout lead Pb_(0.006)Ca_(0.6)Sr_(0.394)Sb₂O₆ Ca_(0.6)Sr_(0.4)Sb₂O₆Luminous density 102 100 (%) Wavelength (nm) 637 638

Results obtained in respect to copper- and/or lead-containingantimonates are shown in table 15.

TABLE 15 optical properties of some copper- and/or lead-containingantimonates excitable by long wave ultraviolet and/or by visible lightand their luminous density in % at about 400 nm excitation wavelengthLuminous density at 400 nm Peak wave Peak wave excitation length oflength of compared lead-/copper- materials Possible compounds not dopedwithout excitation containing materials lead/copper Composition range(nm) copper/lead (%) (nm) (nm) Pb_(0.2)Mg_(0.002)Ca_(1.798)Sb₂O₆F₂:Mn360-400 102 645 649Cu_(0.15)Ca_(1.845)Sr_(0.005)Sb_(1.998)Si_(0.002)O₇:Mn 360-400 101.5 660658 Cu_(0.2)Mg_(1.7)Li_(0.2)Sb₂O₇:Mn 360-400 101.8 652 650Cu_(0.2)Pb_(0.01)Ca_(0.79)Sb_(1.98)Nb_(0.02)O₆:Mn 360-400 98.5 658 658Cu_(0.01)Ca_(1.99)Sb_(1.9995)V_(0.0005)O₇:Mn 360-400 100.5 660 657Pb_(0.006)Ca_(0.6)Sr_(0.394)Sb₂O₆ 360-400 102 637 638Cu_(0.02)Ca_(0.9)Sr_(0.5)Ba_(0.4)Mg_(0.18)Sb₂O₇ 360-400 102.5 649 645Pb_(0.198)Mg_(0.004)Ca_(1.798)Sb₂O₆F₂ 360-400 101.8 628 630

In some embodiments, the lead- and/or copper-containing germanatesand/or germanate-silicates may be generally characterized according toformula (17)a(M′O).b(M″₂O).c(M″X).d(GeO₂).e(M′″O).f(M″″₂O₃).g(M′″″_(o)O_(p)).h(M″″″_(x)O_(y))  (17)

wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be Li,Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M′″ may be Be,Mg, Ca, Sr, Ba, Zn, Cd, and/or any combination thereof; M″″ may be Sc,Y, B, Al, La, Ga, In, and/or any combination thereof; M′″″ may be Si,Ti, Zr, Mn, V, Nb, Ta, W, Mo, and/or any combination thereof; M″″″ maybe Bi, Sn, Pr, Sm, Eu, Gd, Dy, and/or any combination thereof X may beF, Cl, Br, I, and/or any combination thereof 0<a≦2; 0≦b≦2; 0≦c≦10;0<d≦10; 0≦e≦14; 0≦f≦14; 0≦g≦10; 0≦h≦2; 1≦o≦2; 1≦p≦5; 1≦x≦2; and 1≦y≦5.

Example of Preparation

Preparation of the luminescent material having formula (18)Pb_(0.004)Ca_(1.99)Zn_(0.006)Ge_(0.8)Si_(0.2)O₄:Mn  (18)

Starting materials: PbO, CaCO₃, ZnO, GeO₂, SiO₂, MnCO₃, and/or anycombination thereof,

The starting materials in the form of oxides and/or carbonates may bemixed in stoichiometric proportions together with small amounts of flux,for example, NH₄Cl. In a first step the mixture may be fired in analumina crucible at about 1,200° C. in an oxygen-containing atmospherefor about 2 hours. Then, the material may be milled again. In a secondstep the mixture may be fired in an alumina crucible at about 1,200° C.in oxygen containing atmosphere for about 2 hours. After that thematerial may be milled, washed, dried and sieved. The resultingluminescent material may have an emission maximum at about 655 nm.

TABLE 16 lead-containing Mn-activated germanate compared withMn-activated germanate without lead at about 400 nm excitationwavelength Copper-containing compound Comparison without copperPb_(0.004)Ca_(1.99)Zn_(0.006)Ge_(0.8)Si_(0.2)O₄:MnCa_(1.99)Zn_(0.01)Ge_(0.8)Si_(0.2)O₄:Mn Luminous density (%) 101.5 100Wavelength (nm) 655 657

Preparation of the luminescent material having formula (19)Cu_(0.46)Sr_(0.54)Ge_(0.6)Si_(0.4)O₃: Mn  (19)

Starting materials: CuO, SrCO₃, GeO₂, SiO₂, MnCO₃, and/or anycombination thereof.

The starting materials in the form of oxides and/or carbonates may bemixed in stoichiometric proportions together with small amounts of flux,for example, NH₄Cl. In a first step the mixture may be fired in analumina crucible at about 1,100° C. in an oxygen-containing atmospherefor about 2 hours. Then, the material may be milled again. In a secondstep the mixture may be fired in an alumina crucible at about 1,180° C.in an oxygen-containing atmosphere for about 4 hours. After that thematerial may be milled, washed, dried and sieved. The resultingluminescent material may have an emission maximum at about 658 nm.

TABLE 17 copper-containing Mn-activated germanate-silicate compared withMn-activated germanate-silicate without copper at 400 nm excitationwavelength Compound Copper-containing compound without copperCu_(0.46)Sr_(0.54)Ge_(0.6)Si_(0.4)O₃:Mn SrGe_(0.6)Si_(0.4)O₃:Mn Luminousdensity 103 100 (%) Wavelength (nm) 658 655

TABLE 18 optical properties of some copper- and/or lead- dopedgermanate- silicates excitable by long wave ultraviolet and/or byvisible light and their luminous density in % at about 400 mm excitationwavelength Luminous Peak wave density at 400 nm length of Peak waveexcitation lead-/ length of Possible compared with copper- materialsexcitation compounds not doped without range containing materialslead/copper Composition (nm) copper/lead (%) (nm) (nm)Pb_(0.004)Ca_(1.99)Zn_(0.006)Ge_(0.8)Si_(0.2)O₄:Mn 360-400 101.5 655 657Pb_(0.002)Sr_(0.954)Ca_(1.044)Ge_(0.93)Si_(0.07)O₄:Mn 360-400 101.5 660661 Cu_(0.46)Sr_(0.54)Ge_(0.6)Si_(0.4)O₃:Mn 360-400 103 658 655Cu_(0.002)Sr_(0.998)Ba_(0.99)Ca_(0.01)Si_(0.98)Ge_(0.02)O₄:Eu 360-470102 538 533 Cu_(1.45)Mg_(26.55)Ge_(9.4)Si_(0.6)O₄₈:Mn 360-400 102 660657 Cu_(1.2)Mg_(26.8)Ge_(8.9)Si_(1.1)O₄₈:Mn 360-400 103.8 670 656Cu₄Mg₂₀Zn₄Ge₅Si_(2.5)O₃₈F₁₀:Mn 360-400 101.5 658 655Pb_(0.001)Ba_(0.849)Zn_(0.05)Sr_(1.1)Ge_(0.04)Si_(0.96)O₄:Eu 360-470101.8 550 545 Cu_(0.05)Mg_(4.95)GeO₆F₂:Mn 360-400 100.5 655 653Cu_(0.05)Mg_(3.95)GeO_(5.5)F:Mn 360-400 100.8 657 653

In some embodiments, the lead- and/or copper-containing phosphates maybe generally characterized according to formula (20)a(M′O).b(M″₂O).c(M″X).d(P₂O₅).e(M′″O).f(M″″₂O₃).g(M′″″O₂).h(M″″″_(x)O_(y))  (20)

wherein M′ may be Pb, Cu, and/or any combination thereof; M″ may be Li,Na, K, Rb, Cs, Au, Ag, and/or any combination thereof; M′″ may be Be,Mg, Ca, Sr, Ba, Zn, Cd, Mn, and/or any combination thereof; M″″ may beSc, Y, B, Al, La, Ga, In, and/or any combination thereof; M′″″ may beSi, Ge, Ti, Zr, Hf, V, Nb, Ta, W, Mo, and/or any combination thereof;M″″″ may be Bi, Sn, Pr, Sm, Eu, Gd, Dy, Ce, Th, and/or any combinationthereof; X may be F, Cl, Br, I, and/or any combination thereof; 0<a≦2;0≦b≦12; 0≦c≦16; 0<d≦3; 0≦e≦5; 0≦f≦3; 0≦g≦2; 0<h≦2; 1≦x≦2; and 1≦y≦5.

Examples of Preparation

Preparation of the luminescent material having formula (21)Cu_(0.02)Ca_(4.98)(PO₄)₃Cl:Eu  (21)

Starting materials: CuO, CaCO₃, Ca₃(PO₄)₂, CaCl₂, Eu₂O₃, and/or anycombination thereof,

The starting materials in the form of oxides, phosphates, and/orcarbonates and chlorides may be mixed in stoichiometric proportionstogether with small amounts of flux. The mixture may be fired in analumina crucible at about 1,240° C. in reducing atmosphere for about 2hours. After that the material may be milled, washed, dried and sieved.The luminescent material may have an emission maximum at about 450 nm.

TABLE 19 copper-containing doped Eu²⁺-activated chlorophosphate comparedwith Eu²⁺-activated chlorophosphate without copper at about 400 nmexcitation wavelength Compound Copper-containing compound without copperCu_(0.02)Ca_(4.98)(PO₄)₃Cl:Eu Ca₅(PO₄)₃Cl:Eu Luminous density (%) 101.5100 Wavelength (nm) 450 447

TABLE 20 copper- and/or lead-containing phosphates excitable by longwave ultraviolet and/or by visible light and their luminous density in %at about 400 nm excitation wavelength Luminous Peak wave density at 400nm length of Peak wave excitation lead-/ length of Possible comparedwith copper- materials excitation compounds not doped without rangecontaining materials lead/copper Composition (nm) copper/lead (%) (nm)(nm) Cu_(0.02)Sr_(4.98)(PO₄)₃Cl:Eu 360-410 101.5 450 447Cu_(0.2)Mg_(0.8)BaP₂O₇:Eu, Mn 360-400 102 638 635Pb_(0.5)Sr_(1.5)P_(1.84)B_(0.16)O_(6.84):Eu 360-400 102 425 420Cu_(0.5)Mg_(0.5)Ba₂(P,Si)₂O₈:Eu 360-400 101 573 570Cu_(0.5)Sr_(9.5)(P,B)₆O₂₄Cl₂:Eu 360-410 102 460 456Cu_(0.5)Ba₃Sr_(6.5)P₆O₂₄(F,Cl)₂:Eu 360-410 102 443 442Cu_(0.05)(Ca,Sr,Ba)_(4.95)P₃O₁₂Cl:Eu, 360-410 101.5 438, 641 435, 640 MnPb_(0.1)Ba_(2.9)P₂O₈:Eu 360-400 103 421 419

Meanwhile, the phosphor of the light emitting device can comprisealuminate, silicate, antimonate, germanate, phosphate type chemicalcompound, and any combination thereof.

FIG. 6 is one of the embodiment's emission spectrum according to theinvention, which the phosphor is used for the light emitting device. Theembodiment may have a light emitting diode with 405 nm wavelength andthe phosphor, which is mixture of the selected multiple chemicalcompounds in proper ratio. The phosphor may be composed ofCu_(0.05)BaMg_(1.95)Al₁₆O₂₇:Eu which may have peak wavelength at about451 nm, Cu_(0.03)Sr_(1.5)Ca_(0.47)SiO₄:Eu which may have peak wavelengthat 586 nm, Pb_(0.006)Ca_(0.6)Sr_(0.394)Sb₂O₆ Mn⁴⁺ which may have peakwavelength at about 637 nm,Pb_(0.15)Ba_(1.84)Zn_(0.01)Si_(0.99)Zr_(0.01)O₄:Eu which may have peakwavelength at around 512 nm, and Cu_(0.2)Sr_(3.8)Al₁₄O₂₅:Eu which mayhave peak wavelength at about 494 nm.

In such an embodiment, part of the initial about 405 nm wavelengthemission light from the light emitting diode is absorbed by thephosphor, and it is converted to longer 2^(nd) wavelength. The 1^(st)and 2^(nd) light is mixed together and the desire emission is produced.As the shown FIG. 6, the light emitting device convert the 1^(st) UVlight of 405 nm wavelength to wide spectral range of visible light, thatis, white light, and at this time the color temperature is about 3,000Kand CRI is about 90 to about 95.

FIG. 7 is another embodiment's emission spectrum, which the phosphor isapplied for the light emitting device. The embodiment may have a lightemitting diode with about 455 nm wavelength and the phosphor, which ismixture of the selected multiple chemical compounds in proper ratio.

The phosphor is composed of Cu_(0.05)Sr_(1.7)Ca_(0.25)SiO₄:Eu which mayhave peak wavelength at about 592 nm,Pb_(0.1)Ba_(0.95)Sr_(0.95)Si_(0.998)Ge_(0.002)O₄:Eu which may have peakwavelength at about 527 nm, andCu_(0.05)Li_(0.002)Sr_(1.5)Ba_(0.448)SiO₄:Gd, Eu which may have peakwavelength at about 557 nm.

In such an embodiment, part of the initial about 455 nm wavelengthemission light from the light emitting diode is absorbed by thephosphor, and it is converted to longer 2^(nd) wavelength. The 1^(st)and 2^(nd) light is mixed together and the desire emission is produced.As the shown FIG. 7, the light emitting device convert the 1^(st) bluelight of about 455 nm wavelength to wide spectral range of visiblelight, that is, white light, and at this time the color temperature isabout 4,000K to about 6,500K and CRI is about 86 to about 93.

The phosphor of the light emitting device exemplarily described hereincan be applied by single chemical compound or mixture of plurality ofsingle chemical compound besides the embodiments in relation to FIG. 6and FIG. 7, which are explained above.

According to the description above, light emitting device with widerange of color temperature about 2,000K to about 8,000K or about 10,000Kand superior color rendering index of greater than about 60 (e.g.,between about 60 and about 90, or greater than about 90, or betweenabout 90 and about 95) can be realized by using the lead- and/orcopper-containing chemical compounds.

In such a wavelength conversion, the light emitting device exemplarilydescribed herein is capable of use in mobile phones, note book computersand electronic devices such as home appliance, stereo, telecommunicationproducts, as well as in custom display's key pad and back lightapplications. Moreover, the light emitting device exemplarily describedherein can be applied in automobiles, medical instruments andillumination products.

In addition, the chemical compounds exemplarily described herein can beincorporated within paint as a pigment capable of converting wavelengthsof light.

According to the embodiments exemplarily described above, the chemicalcan increase the stability of the light emitting device against water,humidity, vapor as well as other polar solvents.

In the foregoing described embodiments, various features are groupedtogether in a single embodiment for purposes of streamlining thedisclosure. This method of disclosure is not to be interpreted asreflecting an intention that the claimed invention requires morefeatures than are expressly recited in each claim. Rather, as thefollowing claims reflect, inventive aspects lie in less than allfeatures of a single foregoing disclosed embodiment. Thus, the followingclaims are hereby incorporated into this Detailed Description, with eachclaim standing on its own as a separate preferred embodiment of theinvention.

1. A light emitting device, comprising: a light emitting diodeconfigured to emit light; and a phosphor to change a wavelength of thelight, the phosphor covering at least a portion of the light emittingdiode, the phosphor comprising: a compound comprising a host lattice anda luminescent ion, the luminescent ion comprising at least one rareearth element within the host lattice, wherein the host latticecomprises first ions and oxygen, wherein a first portion of the firstions within the host lattice is substituted by divalent copper ions,wherein the compound emits light upon excitation with ultraviolet lightor visible light, and wherein the host lattice comprises an aluminate,an antimonate, a germanate, any combination thereof, or at least one ofan aluminate, an antimonate, a germanate in combination with a silicateor a germanate-silicate.
 2. The light emitting device according to claim1, wherein the compound has the formulaa(M′O).b(M″₂O).c(M″X).d(Al₂O₃).e(M′″O).f(M″″₂O₃).g(M′″″_(o)O_(p)).h(M″″″_(x)O_(y))wherein M′ is Cu, or a combination of Cu and Pb; M″ is Li, Na, K, Rb,Cs, Au, Ag or any combination thereof; M′″ is Be, Mg, Ca, Sr, Ba, Zn,Cd, Mn or any combination thereof; M″″ is Sc, B, Ga, In, or anycombination thereof; M′″″ is Si, Ge, Ti, Zr, Mn, V, Nb, Ta, W, Mo, orany combination thereof; M″″″ is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd,Th, Dy, Ho, Er, Tm, Yb, Lu, or any combination thereof, or at least oneof Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, and Luin combination with at least one of Bi, Sn and Sb; X is F, Cl, Br, I, orany combination thereof; 0<a≦2; 0≦b≦2; 0≦c≦2; 0<d≦8; 0<e≦4; 0≦f≦3;0≦g≦8; 0<h≦2; 1≦o≦2; 1≦p≦5; 1≦x≦2; and 1≦y≦5.
 3. The light emittingdevice according to claim 1, wherein the compound has the formulaa(M′O).b(M″₂O).c(M″X).4-a-b-c(M′″O).7(Al₂O₃).d(B₂O₃).e(Ga₂O₃).f(SiO₂).g(GeO₂).h(M″″_(x)O_(y)) wherein M′ is Pb, Cu, or any combination thereof; M″ is Li, Na,K, Rb, Cs, Au, Ag, or any combination thereof; M′″ is Be, Mg, Ca, Sr,Ba, Zn, Cd, Mn, or any combination thereof; M″″ is Sc, Y, La, In, Ce,Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, or any combinationthereof, or at least one of Sc, Y, La, In, Ce, Pr, Nd, Pm, Sm, Eu, Gd,Tb, Dy, Ho, Er, Tm, Yb, Lu in combination with at least one of Bi, Snand Sb; X is F, Cl, Br, I, or any combination thereof; 0<a≦4; 0≦b≦2;0≦c≦2; 0≦d≦1; 0≦e≦1; 0≦f≦1; 0≦g≦1; 0<h≦2; 1≦x≦2; and 1≦y≦5.
 4. The lightemitting device according to claim 1, wherein the compound has theformulaa(M′O).b(M″O).c(Al₂O₃).d(M′″₂O₃).e(M″″O₂).f(M′″″_(x)O_(y)) wherein M′ isCu, or a combination of Cu and Pb; M″ is Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn,or any combination of thereof; M′″ is B, Ga, In, or any combinationthereof; M″″ is Si, Ge, Ti, Zr, Hf, or any combination thereof; M′″″ isSc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, orany combination thereof, or at least one of Sc, Y, La, Ce, Pr, Nd, Pm,Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, and Lu in combination with at leastone of Bi, Sn and Sb; 0<a≦1; 0≦b≦2; 0<c≦8; 0≦d≦1; 0≦e≦1; 0<f≦2; 1≦x≦2;and 1≦y≦5.
 5. The light emitting device according to claim 1, whereinthe silicate or germanate-silicate has the formulaa(M′O).b(M″O).c(M′″X).d(M′″₂O).e(M″″₂O₃).f(M′″″_(o)O_(p)).g(SiO₂).h(M″″″_(x)O_(y))wherein M′ is Cu, or a combination of Cu and Pb; M″ is Be, Mg, Ca, Sr,Ba, Zn, Cd, Mn, or any combination thereof; M′″ is Li, Na, K, Rb, Cs,Au, Ag, or any combination thereof; M″″ is Al, Ga, In, or anycombination thereof; M″″ is Ge, V, Nb, Ta, W, Mo, Ti, Zr, Hf, or anycombination thereof; M″″″ is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb,Dy, Ho, Er, Tm, Yb, Lu, or any combination thereof, or at least one ofSc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu incombination with at least one of Bi, Sn and Sb; X is F, Cl, Br, I, orany combination thereof; 0<a≦2; 0<b≦8; 0≦c≦4; 0≦d≦2; 0≦e≦2; 0≦f≦2;0<g≦10; 0<h≦5; 1≦o≦2; 1≦p≦5; 1≦x≦2; and 1≦y≦5.
 6. The light emittingdevice according to claim 1, wherein the compound has the formulaa(M′O).b(M″₂O).c(M″X).d(Sb₂O₅).e(M′″O).f(M″″_(x)O_(y)) wherein M′ is Pb,Cu, or any combination thereof; M″ is Li, Na, K, Rb, Cs, Au, Ag, or anycombination thereof; M′″ is Be, Mg, Ca, Sr, Ba, Zn, Cd, Mn, or anycombination thereof, M″″ is Sc, Y, La, Pr, Sm, Eu, Tb, Dy, Gd, or anycombination thereof, or at least one of Sc, Y, La, Pr, Sm, Eu, Tb, Dy,Gd in combination with at least one of Bi and Sn; X is F, Cl, Br, I, orany combination thereof; 0<a≦2; 0≦b≦2; 0≦c≦4; 0<d≦8; 0≦e≦8; 0≦f≦2;1≦x≦2; and 1≦y≦5.
 7. The light emitting device according to claim 1,wherein the compound has the formulaa(M′O).b(M″₂O).c(M″X).d(GeO₂).e(M′″O).f(M″″₂O₃).g(M′″″_(o)O_(p)).h(M″″″_(x)O_(y))wherein M′ is Pb, Cu, or any combination thereof; M″ is Li, Na, K, Rb,Cs, Au, Ag, or any combination thereof; M′″ is Be, Mg, Ca, Sr, Ba, Zn,Cd, or any combination thereof; M″″ is Sc, Y, B, Al, La, Ga, In, or anycombination thereof; M′″″ is Si, Ti, Zr, Mn, V, Nb, Ta, W, Mo, or anycombination thereof; M″″″ is Pr, Sm, Eu, Gd, Dy, or any combinationthereof, or at least one of Pr, Sm, Eu, Gd, Dy in combination with atleast one of Bi and Sn; X is F, Cl, Br, I, or any combination thereof;0<a≦2; 0≦b≦2; 0≦c≦10; 0<d≦10; 0≦e≦14; 0≦f≦14; 0≦g≦10; 0≦h≦2; 1≦o≦2;1≦p≦5; 1≦x≦2; and 1≦y≦5.
 8. The light emitting device according to claim1, wherein the compound has the formulaa(M′O).b(M″₂O).c(M″X).d(P₂O₅).e(M′″O).f(M″″₂O₃).g(M′″″O_(2).)h(M″″″_(x)O_(y)) wherein M′ is Cu, or a combination of Cu and Pb; M″ isLi, Na, K, Rb, Cs, Au, Ag, or any combination thereof; M′″ is Be, Mg,Ca, Sr, Ba, Zn, Cd, Mn, or any combination thereof; M″″ is Sc, Y, B, Al,La, Ga, In, or any combination thereof; M′″″ is Si, Ge, Ti, Zr, Hf; V,Nb, Ta, W, Mo, or any combination thereof, M″″″ is Pr, Sm, Eu, Gd, Dy,Ce, Th, or any combination thereof, or at least one of Pr, Sm, Eu, Gd,Dy, Ce and Th in combination with at least one of Bi and Sn; X is F, Cl,Br, I, or any combination thereof; 0<a≦2; 0≦b≦12; 0≦c≦16; 0<d≦3; 0≦e≦5;0≦f≦3; 0≦g≦2; 0.01<h≦2; 1≦x≦2; and 1≦y≦5.
 9. The light emitting deviceaccording to claim 1, further comprising a sealing material to cover thelight emitting diode and the phosphor.
 10. The light emitting deviceaccording to claim 1, wherein the phosphor is mixed with a hardeningmaterial.
 11. The light emitting device according to claim 1, furthercomprising: a substrate; a plurality of electrodes arranged on thesubstrate; and an electrically conductive device to connect the lightemitting diode with one of the plurality of electrodes, wherein thelight emitting diode is arranged on another of the plurality ofelectrodes.
 12. The light emitting device according to claim 1, furthercomprising: a plurality of leads; a diode holder arranged at the end ofone of the plurality of leads; and an electrically conductive device toconnect the light emitting diode with another of the plurality of leads,wherein the light emitting diode is arranged in the diode holder andcomprises a plurality of electrodes.
 13. The light emitting deviceaccording to claim 1, further comprising: a housing; a heat sink atleast partially arranged in the housing; a plurality of lead framesarranged on or around the heat sink; and an electrically conductivedevice to connect the light emitting diode with one of the plurality oflead frames, wherein the light emitting diode is arranged on the heatsink.
 14. A light emitting device, comprising: a light emitting diodeconfigured to emit light; and a phosphor to change a wavelength of thelight, the phosphor covering at least a portion of the light emittingdiode, the phosphor comprising: a compound comprising a host lattice anda luminescent ion, the luminescent ion comprising at least one rareearth element within the host lattice, wherein the host latticecomprises first ions, silicon, and oxygen, wherein a first portion ofthe first ions within the host lattice is substituted by divalent copperions, wherein the compound emits light upon excitation with ultravioletlight or visible light, wherein the host lattice comprises first ions,silicon, and oxygen, and wherein the compound comprises a trigonalGlaserite structure, a monoclinic Merwinite structure, a tetragonalcrystal structure, or an orthorhombic crystal structure.